The synthesis of 5,5-bi-(dipyrromethenyls) and related compounds

Dolphin, David; Harris, R.; Huppatz, John L.; Johnson, A. W.; Kay, I. T.; Leng, Ji‐Dong

doi:10.1039/j39660000098

Cited by 31 publications

(24 citation statements)

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“…25), 510 (4.14), 542 (3.58), 576 (3.75), 628 (3.36); UV/vis (5% TFA-CHCl 3 ): λ max [nm] (log 10 ε) 416 (5. The mixture was diluted with dichloromethane (19 ml), followed immediately by the addition of 3,4-diethyl-1H-pyrrole-2,5-dicarboxaldehyde (39.5 mg), and the resulting mixture was stirred for a further 2 h under nitrogen.…”

Section: 37121318-hexaethyl-817dimethylporphyrin (16)mentioning

confidence: 99%

“…In particular, MacDonald [8] demonstrated that 5,5'-diunsubstituted dipyrrylmethanes 1a, or the related dicarboxylic acids 1b, condense with dipyrrylmethane dialdehydes 2 in the presence of strong acid catalysts (e.g. Alternative strategies have been developed for the stepwise synthesis of totally asymmetrical porphyrin structures, involving a-oxobilane [21], b-oxobilane [22], b-bilene [23], tripyrrene [24] or a,c-biladiene [25] intermediates, although the increased number of steps involved leads to a decrease in the overall yields obtained. This versatile methodology has been applied to the synthesis of many different porphyrin structures, including uroporphyrins [8], coproporphyrins [10], protoporphyrins [11] cycloalkanoporphyrins [12][13][14], naphthoporphyrins [15] and phenanthroporphyrins [16].…”

Section: Introductionmentioning

confidence: 99%

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Porphyrins with exocyclic rings. Part 9 [1] Synthesis of porphyrins by the ‘3 + 1’ approach

Lash¹

1997

J. Porphyrins Phthalocyanines

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Tripyrrane dibenzyl esters are readily available from the reaction of two equivalents of 5-acetoxymethylpyrrole-2-carboxylates with 2,5-diunsubstituted pyrroles in refluxing acetic acid-ethanol. Hydrogenolysis of the benzyl ester moieties affords the corresponding dicarboxylic acids, and subsequent condensation with 2,5-diformylpyrroles in 5% trifluoroacetic acid-dichloromethane, followed by neutralization with triethylamine and oxidation with DDQ, gives porphyrin products in good to excellent yields. The isomeric purity of these products has been rigorously demonstrated by proton and carbon-13 NMR spectroscopy. This chemistry allows the direct synthesis of porphyrin structures that would otherwise only be accessible via multistep procedures. In addition, this approach provides a convenient synthetic entry to the geochemically important tetrahydrobenzoporphyrins and cycloalkanoporphyrins. The first examples of tripyrranes with tetrahydroindole subunits are reported and their utility in the synthesis of novel cycloalkanoporphyrins is disclosed.

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Section: 37121318-hexaethyl-817dimethylporphyrin (16)mentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Porphyrins with exocyclic rings. Part 9 [1] Synthesis of porphyrins by the ‘3 + 1’ approach

Lash¹

1997

J. Porphyrins Phthalocyanines

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“…20 Along these lines, we recently prepared a 10,10-dimethylbiladiene (DMBil) framework as a stable nonmacrocyclic tetrapyrrole. In addition to probing the basic light absorbing and redox properties of the DMBil platform, we also showed that this platform can ligate zinc(II) and copper(II) centers.…”

Section: Introductionmentioning

confidence: 99%

Electrochemical, Spectroscopic, and¹O₂Sensitization Characteristics of Synthetically Accessible Linear Tetrapyrrole Complexes of Palladium and Platinum

et al. 2017

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The synthesis, electrochemistry, and photophysical characterization of a 10,10-dimethyl-5,15-bis(pentafluorophenyl)-biladiene (DMBil1) linear tetrapyrrole supporting PdII or PtII centers is presented. Both of these nonmacrocyclic tetrapyrrole platforms are robust and easily prepared via modular routes. X-ray diffraction experiments reveal that the Pd[DMBil1] and Pt-[DMBil1] complexes adopt similar structures and incorporate a single PdII and PtII center, respectively. Additionally, electrochemical experiments revealed that both Pd[DMBil1] and Pt[DMBil1] can undergo two discrete oxidation and reduction processes. Spectroscopic experiments carried out for Pd[DMBil1] and Pt[DMBil1] provide further understanding of the electronic structure of these systems. Both complexes strongly absorb light in the UV–visible region, especially in the 350–600 nm range. Both Pd[DMBil1] and Pt[DMBil1] are luminescent under a nitrogen atmosphere. Upon photoexcitation of Pd[DMBil1], two emission bands are observed; fluorescence is detected from ~500–700 nm and phosphorescence from ~700–875 nm. Photoexcitation of Pt[DMBil1] leads only to phosphorescence, presumably due to enhanced intersystem crossing imparted by the heavier PtII center. Phosphorescence from both complexes is quenched under air due to energy transfer from the excited triplet state to ground state oxygen. Accordingly, irradiation with light of λ ≥ 500 nm prompts Pd[DMBil1] and Pt[DMBil1] to photosensitize the generation of 1O2 (singlet oxygen) with impressive quantum yields of 80% and 78%, respectively. The synthetic accessibility of these complexes coupled with their ability to efficiently photosensitize 1O2 may make them attractive platforms for development of new agents for photodynamic therapy.

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“…From molecular mass determination, the latter were deduced to exist in two different, interchangeable forms, namely the coordination modes displayed by 1 and 2 (Scheme 1). [7] In this context, we had two important questions. Firstly, what is the impact of elongated MϪN bonds of e.g.…”

Section: Introductionmentioning

confidence: 99%

Structural and Spectroelectrochemical Studies on (2,2′-Bidipyrrinato)copper(II) and -palladium(II) Complexes

Bröring

Brandt

Bley-Escrich³

et al. 2002

Eur. J. Inorg. Chem.

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Copper(II) and palladium(II) complexes of two 2,2′‐bidipyrrin ligands were prepared and examined, in comparison with the known nickel(II) complexes of these ligands, by means of X‐ray crystallography, cyclic voltammetry, and spectroelectrochemistry. All compounds are of helical geometry with coordination environments of the metal centres displaying very small tetrahedral distortions for palladium and very large ones for copper complexes. Porphyrinoid behaviour was found for the one‐ and two‐electron oxidations of all complexes studied, as well as for the reductions of the PdII species. On the other hand, the reduction of the CuII complexes shows some special features, which may be explained from the results of spectroelectrochemical studies as related to the particular non‐planarity of these compounds. (© Wiley‐VCH Verlag GmbH, 69451 Weinheim, Germany, 2002)

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The synthesis of 5,5-bi-(dipyrromethenyls) and related compounds

Cited by 31 publications

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Porphyrins with exocyclic rings. Part 9 [1] Synthesis of porphyrins by the ‘3 + 1’ approach

Porphyrins with exocyclic rings. Part 9 [1] Synthesis of porphyrins by the ‘3 + 1’ approach

Electrochemical, Spectroscopic, and¹O₂Sensitization Characteristics of Synthetically Accessible Linear Tetrapyrrole Complexes of Palladium and Platinum

Structural and Spectroelectrochemical Studies on (2,2′-Bidipyrrinato)copper(II) and -palladium(II) Complexes

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The synthesis of 5,5-bi-(dipyrromethenyls) and related compounds

Cited by 31 publications

References 0 publications

Porphyrins with exocyclic rings. Part 9 [1] Synthesis of porphyrins by the ‘3 + 1’ approach

Porphyrins with exocyclic rings. Part 9 [1] Synthesis of porphyrins by the ‘3 + 1’ approach

Electrochemical, Spectroscopic, and1O2Sensitization Characteristics of Synthetically Accessible Linear Tetrapyrrole Complexes of Palladium and Platinum

Structural and Spectroelectrochemical Studies on (2,2′-Bidipyrrinato)copper(II) and -palladium(II) Complexes

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Electrochemical, Spectroscopic, and¹O₂Sensitization Characteristics of Synthetically Accessible Linear Tetrapyrrole Complexes of Palladium and Platinum